Treatment of hydrocarbon oils



April 1,0, 1934. J. c. MORRELL E'r AL TREATMENT 0F HYDROCARBON QILS y a. @n ,1 w Q6, @M .4! @f 5 f 0? W m 7 3. W w C? m im n a u Ww n w m w .m 0&3 u., w 3 5 we .h 9 @my m h Z of w 3f ,w m@ f @fof/ um* 2 ML .l 00 d W@ .W9 la w 3 6 2 Patented Apr. 10, 1.934

UNITED STATES c PATENT OFFICE l 1,954,486 TREATMENT oF mmRocAnBoN olLs Jacque C. Morrell and Gustav Eglofl, Chicago, Ill., assignors to Universal Oil Products Company,. Chicago, Ill., a corporation of South Pakt* Application :une s, 1931,l serial No; 541,774

4 claims.V (01196-36) lo methods which refine the Avapors prior to their condensation so that the condensed liquids require no redistillation and a minimum of further c treatment.

In one specific embodiment the invention' comprises treating hydrocarbon oil vapors with hydrochloric acid and solutions oi zinc chloride in the presence of salts of copper and solid contact substances which exert catalytic, polymerlzing or chemical iniluences -upon the Vcourse oi vthe reaczo tions.

Various salts of copper are adaptable to use in solid form according to the process of the present invention, these salts being mixed with or deposited upon either inert or active spacing materials, the leffects obtained by the use of any particular salt varying in degree depending upon the nature of the salt and upon other factors such as its solubility under the conditions of operation in the zinc chloride solutionswhich are used. According to the process of the invention it is preierred to loperate with solutions of zinc chloride saturated both with respect to'zinc chloride and the particular copper salt or salts used in the solid form sothat a denite ratiooi dissolved to solid saltv is maintained. As examples ofthe more soluble salts of copper may be mentioned cupric chloride, cupric' bromide, cuprlc nitrate, cupric acetate, cupric formate, cupric sulfate, etc. The corresponding cuprous salts are generally either 40 insoluble or only slightly soluble in water oraqueous solution and in this respect may be readily adaptable to use in the present process without fear of removal by the solutions of zinc chloride. As examples oi solid contact materials which may be employed in combination with hydrochloric acid and zinc chloride solutionsand solid salts of copper may be mentioned such materials asv clays, fullers earth, bentonite, bauxite, certain types of the zeolites such as greensand or glauconite, silica gel, etc., these substances containing at times minor amounts of finely divided metals or their oxides. Attimesit may be also desirable to employ the metals or metal oxidesas principal constituents or the contact masses-and 'su une beds or material through which-the ou vapors pass during treatment may be uniform throughout the mass or grade into strata of variable composition. As a further means of securing effective contact materials may at times be supported upon superimposed trays.

To assist in describing operations typical of the process of the present invention the attached diagrammatic drawing has been provided which represents arrangements of vequipment in which operations may be conducted, Figure 1 represent- 65 ing a layout adaptable to use when the oil vapors pass downwardly with the hydrochloric acid Vand zinc chloride solution through the contact mass containing copper salts and Figure 2 a layout whichv may be used when 'best results are ob- ,70 tained with passage of the oil vapors mixed with hydrochloric acid upwardly through the contact masses'counteriiow to the zinc chloride solutions.

Referring to Figure 1, line 1 containing a control valve 2 may represent a supply line for hy- 75 drocarbon oil vapors to be treated which may come from any oil refining process in which relatively low boiling hydrocarbon vapors are generated such as a primary distillation or a cracking process, such vapors with or withouty substantial pressure reduction being admitted to the upper section 11 of a treater 3 which contains a suitable bed of solid contact materials l2 containing solid salts of copper supported upon a perforated false bottom 12 which separates the solid 85 materials from a lower space 13. Hydrochloric acid either in aqueous solution or as a gas may be introduced into the oil vapors through a line 4 containing control valve 5 into vapor space 1l, and line 6 containing valve '7 and terminating in 90 'a spray or other distributing means 10 may be used as a source of supply for the zinc chloride solutions which may bepumped in by means not shown at a rate consistent with the production .of desired treating effects. B ranch line '8 contain- 95 inga valve 9 may serve for the-admission of other metallic salt solutions such as, for example, solutions of salts of copper necessary to be added to the zinc chloride solution to substantially prevent a reduction in the solid phase. of the copper salts and a line 20 containing control valve v21 permits the recirculation of partially spent solutions as will be presently more fully described. The reactions occurring during the passage of oil vapors, hydrochloric acid and zinc chloride solution through the typesI of contact masses mentioned are of a complicated nature which vary markedly in degree depending upon numerous chemical and physical factors such as, for

example, the composition of the entering oilvapors, ll0

the amount of hydrochloric acid used, the particular solid salts of copper used and the concentration of the entering zinc chloride solution and the nature of the contact mass. However., the effect of this type of treatment upon oil vapors produces very definite results in controllable reduction of olenic unsaturation, particularly vthose unsaturated compounds which tend to form gums, and reduction in sulphur content, a considerable portion of the sulphur in the oil vapors being eliminated as hydrogen sulphide and lother portions being removed in heavy polymerized bodies formed.

The treated vapors along with reaction products and spent or partially spent salt solutions fall into lower chamber 13 wherein separation of vapors and liquids is effected. Liquids which include the salt solutions and heavy hydrocarbon reaction products substantially immiscible therewith may pass together through a line 14 controlled by a valve 15 to a separator 16, Ycooling being effected if further advisable by passing through intermediate cooling coils not shown in the drawing. In separator 16 partially spent salt solutions may separate as a lower layer and in case they still retain some virtue as treating reagents may be taken by circulating pump 19 through a line 17 containing control valve 18 and discharged back into the stream of incoming vapors by way of line 20 containing control valve 21 and line 7 as already mentioned. If it be found that the solutions are ineiective for further treatment they may be discharged through a line 22 containing a valve 23 for suitable disposal or the regeneration of active constituents. Liquid hydrocarbon products such as heavy polymerized oils which may appear as a layer above the aqueous layer may be taken from the separator through a line 33 containing a valve 34 to a pump 35 which discharges into a line 38 containing a control valve 39, which line may lead to a suitable point of disposal or use for these products, or may return them, for example, to a suitable point in a cracking unit from which the original oil vapors may have come so that they are further converted to produce increased yields of light desirable products, gases separating in separator 16 which may contain hydrochloric acid and low boiling chlorine derivatives of hydrocarbons may be withdrawn from the system to any point desired to a line 24 at a rate controlled by valve 25. The hydrochloric acid may be recovered by water absorption if such recovery is economical or 'it may be neutralized if such is not the case by such substances as caustic soda or ammonia. Line 26 is shown leading -from the gas line 24 back into the separating chamber 13 of treater 3 to permit l,vapor connection therewith and prevent gas lock which might interfere with the free passage of liquids through line 14 to the separator 16.

Vapors from chamber 13 in the bottom of treater 3 may be conducted through a line 27 controlled by a valve 28 with or without further pressure reduction to a nal fractionator 29, which is capable of producing low boiling hydrocarbon fractions of the range necessary for gasoline. Reuxes from'this fractionator may pass through a line 30 controlled by alvalve 31 to a receiver 32 which is also in liquid connection with pump through line 36 containing valve 37 so that these refluxes may be disposed of jointly with the liquid separated in the bottom of the treater. These refluxes may also be subjected to intermediate cooling by means not shown as in the Case 0f those I from the treater.

Vapors of desired boiling point range along with incondensible gases vmay pass from fractionator 29 through a vapor line 40 controlled by a valve 41 and be cooled during passage through a condenser 42, the cooled products passing through a line 43 controlled by a valve 44 to a receiver and separator 45 which has a gas release line 46 containing control valve 47 and liquid draw line 48 containing control valve 49 which may be utilized for disposing of treated liquids. To assist in controlling the boiling point of vapors emergent from fractionator 29 a suitable amount of these liquids may be returned from receiver 45 to the top of the fractionator by equipment not shown. To keep down corrosion effects in the fractionating, condensing and collecting equipment ammonia or neutralizing materials may be introduced to the system at any point following the treater, the exact amounts necessary and the best point of introduction being determined by trial.

Referring to Figure 2, a slightly altered type of equipment is shown in which the treatment of the oil vapors is conducted generally counterflow to the zinc chloride solution. In this drawing line 51 containing valve 52 indicates the line and valve through which hydrocarbon vapors may be admitted to the process similarly to those admitted in the preceding figure, such vapors entering lower compartment 56 of treater 55 and passing up through'solid contact mass 57 containing copper salts supported upon a perforated false bottom 57. Hydrochloric acid may be admitted vto the vapors through a-line 53 containing control valve 54. The zinc chloride solution may be admitted to vapor space 58 above the contact mass in the treater from a line 59 containing a valve 60, this line terminating in a spray or other atomizing means 61.

'I'he essential differences between this type of treatment counterow to the salt solutions and the concurrent treatment described in connection with Figure 1 are that first, the rising vapors undergo a` partial fractionation and second, that the chemical treatment may be at times more effective due to the counterflow action. However,

since both types of ilow are adaptable in different cases, it is not intended to confine the invention to either case. As before, fin connection with Figure 1, heavy hydrocarbon liquids and reaction products and spent' or partially spent treating solutions may accumulate in lower chamber 56, these passing through a line 62 containing a valve 63 to a separator 64 in which the same general types of separation and segregation occur as in separator 16 of Figure 1. As before, spent or partially spent salt solutions may be removed through a line 65 containing control valve 66 and pumped by a pump 67 through a line 68 containing a valve 69 either back to the pn'mary spray line 59 or containing a valve 71. The liquid layer of hydrocarbons and reaction products may be taken from above the aqueous layer through'a line 88 containing a valve 89 and discharged by a pump 87 through a line 90 containing a valve 91 to the heating zone of a conversion process or to storage. Gases from the separator may be released through a line 72 containing a Valve 73, and gas lock may be prevented as before by the provision of a line 74 connecting the vapor spaces.

Vapors from treater 55 may pass throughl a line 75 containing a valve 76 and in case further fractionation is necessary to obtain low boiling liquids of desired boiling point range, they may be passed through la line 77 controlled by a valve 78 to a final fractionator 8 1. Heavy reuxes may be withdrawn through a line82 containinga valve 83 to a receiver 84 whence they are admitted to pump 87 through a line 85 controlled by a valve 86 and disposed of along with the hydrocarbon liquids from separator 64. Fixed gases and vapors of desired boiling point range may leave the top of fractionator 81 through a line 92 controlled by a valve 93 and byway of a line 94 containing a valve 95 to a condenser 96 from whence the cooled products pass througha line 97 controlled by a. valve 98'to a receiver 99, this receiver having the usual gas vent line 100 controlled by a valve 101 and a liquid draw line 102 controlled by valve 103 for finished products. Portions of the finished liquids may be returned to the top of the fractionator tol control the fractionation therein by means of lines and pumps not shown in the present drawing.

When suiiicient fractionation has been effected during the pesage of the oil vapors upwardly through treater 55, the fractionator 81 may be bypassed, the vapors from line controlled by valve 76, being conducted through a line 79 containing a control valve directly to line 94 and thence to the condensing and collecting equipment as already described. Y

As examples of operations comprised within the scope of the invention many cases might be cited but it will suiice to give three typical of treatments of' vapors of cracked gasolines produced when operating upon charging oils from the Pennsylvania, California and Texas fields.

In the case of the Pennsylvania vstock the vapors may be passed upwardly through a tower containing finely divided clay or earth mixed with 10 to 20% by Wleight of. solid cupric chloride countercurrent to a solution .saturated both with respect to zinc chloride and cupric chloride, the oil vapors being mixed with hydrochloric acid at the rate of 1 pound of concentrated or 37% acid per barrel of distillate, a small amount of air and suilicient steam to overcome the effect of v aporization of water from the solution. Condensed distillate from this treatment may have a gum content of -from 10 to 20 rngs. by the copper dish method whereas the distillates produced Without the treatment may have a gum content as high as 275 mgs. The distillate after treatment will -have good color and stability.

By a similar operation upon vapors of gasoline boiling point range produced in the cracking of a California gas oil, the amount pf hydrochloric acid being increased to 11/2 pounds per barrel, the treatment maysreduce the gum content from 400 mgs; to 20 mgs. and at 'the same ltime reduce the sulphur content from 0.3% to 0.1%, the gasoline being sweet to the doctor test and having good color and color stability. e

Cracking operations upon a residuum from the Refugio eld of east Texas may produce a gasoline containing as high as 900 mgs. of gum per f 100 cc. and sulphur as high as 0.4%. By treating the vapors of such a distillate by the process ofthe invention using hydrochloric acid at the.

rate of 2 pounds per barrel and operating in the general manner described in the two preceding examples, the gum content may be reduced to 50 mgs'. and the sulphur content to approximately 0.1%. Y

The foregoing general description and examples of results obtainable bythe process of the invention will serve to indicate the commercial advantages thereof but since the invention is broad in scope andl may be operated in many other ways than the ones disclosed, the description and examples are not to be taken in'a limiting sense.

lWe lclaim as our invention:

1. A process for refining hydrocarbon vapors which comprises treating the same with hydro- 1 chloric acid in the presence of aqueous zinc chloride solution and a copper salt in solidform.

2. A process for "rening hydrocarbon vapors which comprises treating the same with hydrochloric acid in the presence of a copper salt in solid form and an aqueous zinc chloride solution containing dissolved copper salt.

v3.jl process for rening hydrocarbon vapor which comprises treating the same'with hydrochloric acid in the presence of aqueous zinc chlo-n ride solution and an earthy adsorbent containing a copper salt in solid form.

4. A process for refining hydrocarbon vapors which comprises treating the same with hydro- 'i chloric acidl in the presence of aqueous zinc chloride solution and a copper chloride in solid form.

JACQUE c. MORREH.. GUs'rAv EGLOFF. 

